1. Field of the Invention
This invention relates to new polymers and prepolymers derived from polyoxyalkyleneamines. The polymers and prepolymers may be used in a process for the treatment of wool so as to impart shrink resistance.
2. Description of the Prior Art
The polyoxyalkyleneamines of interest are a family of polyamines which have as their backbone repeated oxyalkylene units. Such materials have been available commercially for a number of years, for example, under the trade name of Jeffamines (Jeffamine is a registered trade mark). Belgian Patent No. 634,741 describes the preparation of polyoxyalkyleneamines by the reductive amination of polypropylene glycol ether with ammonia in the presence of Raney nickel catalyst and hydrogen. U.S. Pat. Nos. 3,236,895 and 3,462,393 teach the synthesis of polyoxy alkyleneamines by the amination of polypropylene glycol via a sulphonic acid ester. In U.S. Pat. No. 3,654,370 polyoxyalkyleneamines are produced by treating the corresponding polyol with ammonia and hydrogen over a nickel/copper/chromium catalyst.
The polyoxyalkyleneamines have found a variety of uses. They are particularly effective as epoxy curing agents and have been used in epoxy adhesives, protective or decorative coatings and reinforced composites. Other applications include use in anti-static agents, surfactants, agricultural chemicals, cosmetics, oil recovery chemicals and textile treating agents.
With regard to the latter application, that of textile treating agent, polyoxyalkyleneamines have been applied to a variety of fibres and textiles for various purposes. For example, German OS 2,645,954 describes the improvement of crease, abrasion and pilling resistance of wool textiles by the use of linking agent amines (such as Jeffamine D-400) during the shrinkproofing of such textiles. However, the polyoxyalkyleneamine is used as a catalyst for the crosslinking of epoxy groups, following the application of resins from perchloroethylene, and its association with shrinkproofing treatment itself is merely incidental. British Patent No. 942,875 refers to the formation of water-soluble anti-static coatings for fibres by reacting polyoxy alkylenediamines with aldehydes. U.S. Pat. No. 3,17 5,987 discloses the reaction of polyethylene glycoldiamine with an epoxide for the purpose of treating nylon cloth so as to resist soiling. German OS 2,058,317 refers to the reaction of a triethylene glycoldiamine with urea to form a permanent press fabric treatment.
Japanese Patent No. 71/33,152 describes the treatment of a nylon textile with an E-caprolactam-polyethylene glycol diamine-adipic acid copolymer to give improved washfast stain resistance, while Japanese Patent No. 71/37,675 relates to the melt-blending of a polyester fibre with a hexamethylenediammonium terephthalate-E-caprolactamdiamino-polyethylene glycol-adipic acid copolymer for the purpose of improving dyeability. U.S. Pat. No. 3,738,864 discloses that the treatment of fibres with the reaction product of a polyoxypropylenediamine (jeffamine D-1000) and a polyepoxide results in material with durable anti-static properties. U.S. Pat. No. 4,255,311 describes a composition useful for treatment of textiles so as to prevent creasing and which was prepared from a water-soluble epoxide resin, an acrylic copolymer and a polyoxyalkylene polyamine. U.S. Pat. No. 3,676,287 teaches that adhesion in glass fibre-reinforced elastomers can be improved by coating the fibres with a mixture which includes a lubricant prepared by condensing Jeffamine D-2000 with oleic acid.
Japanese Patent No. 84/89325 describes high rigidity resin compositions formed from a mixture of poly(phenyleneterephthalamide)-epichlorohydrin reaction product, Jeffamine D-230 and Jeffamine AC-398. U.S. Pat. No. 4,382,852 relates to demulsifiers for breaking bituminous oil-in-water emulsions and which are prepared by the condensation of certain polyoxyalkylenediamines (i.e. Jeffamines ED-2001, ED-600, ED-900, M-1000, D-230 and M-360) with epichlorohydrin. J. Med. Chem., 26(1), 7-11 refers to the preparation of compounds by the reaction of aryl glycidyl ethers with various Jeffamines and the evaluation of their affinity for .beta.-adrenergic receptors of rat heart and lung. U.S. Pat. No. 4,323,709 discloses the reaction of epichlorohydrin with Jeffamine M-600 to give polymers useful as hydrocarbon oil additives. U.S. Pat. No. 4,239,497 describes fuel oil stabilising agents which inhibit sedimentation and discolouration during storage and are manufactured by the reaction of epichlorohydrin with amine-terminated polyoxypropylenes such as Jeffamine M-600. There is no suggestion in the prior art that any of these products could be used as shrink-resist polymers in processes for imparting a degree of shrink resistance to wool.
Many ways of rendering wool shrink resistant are known. Typically, these involve subjecting the wool to an oxidative treatment, either alone or followed by a polymer treatment. The latter type of two-step treatment has become very popular and is now the major process used throughout the world.
Various two-step shrink-proofing processes in which wool is treated first with an oxidative chlorinating agent and subsequently with a pre-formed synthetic polymer have been developed. A wide variety of polymers can be used in aqueous solution or dispersion, including polyamide-epichlorohydrin resins and polyacrylates. A review of work in this field by J. Lewis appears in Wool Science Review, May 1978, pages 23-42. British Patent Nos. 1,074,731 and 1,340,859 and U.S. Pat. Nos. 2,926,154 and 2,961,347 describe two-step shrink-proofing processes and resins or polymers suitable for use therein. These polymers are typically reactive polyamides. The polyamides can be derived from a polyalkylene polyamine and a dicarboxylic acid, e.g. diethylenetriamine and adipic acid, and are prepared by reaction with epichlorohydrin.
These conventional two-step processes confer good levels of shrink resistance but, despite achieving considerable commercial success, they do have significant disadvantages. It will be appreciated that the polymer is added to the oxidised wool to supplement the shrink resistance imparted by the oxidative pretreat, which may in some cases thus not be as severe as would be needed if this were the only treatment used to achieve the shrink resistance. The application of polymers, however, usually results in wool which has an undesirably harsh handle. To overcome this problem a softening agent is customarily employed during subsequent processing of the wool. Further, if the wool which has been treated with polymer is then dyed, the resulting rub fastness is generally inferior. This is particularly evident with certain dyestuffs commonly used in the wool industry. In general, it is found that the softening agents which are used to improve the handle of the wool will either exacerbate the poor rub fastness or are removed during the dyeing operation.